CN109763143A - A kind of processing method for resource recovery of waste lead acid battery - Google Patents
A kind of processing method for resource recovery of waste lead acid battery Download PDFInfo
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- CN109763143A CN109763143A CN201910056433.1A CN201910056433A CN109763143A CN 109763143 A CN109763143 A CN 109763143A CN 201910056433 A CN201910056433 A CN 201910056433A CN 109763143 A CN109763143 A CN 109763143A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention belongs to waste lead acid battery resource utilization process fields, more particularly, to a kind of processing method for resource recovery of waste lead acid battery.Waste lead acid battery is treated as high-purity methylsulfonic acid lead by the innovation wet processing that whole process does not generate extra low value by-product by the present invention, and it is electrolysed using this methane sulfonic acid lead as electrolyte, cathode obtains high-purity lead bullion, and anode obtains the ti-supported lead dioxide electric coated electrode with high added value.The present invention is combined by that will innovate wet process lead recovery process with lead dioxide electrode preparation process, reduces the added value that recovery product is improved while unwanted byproduct generates.It solves the high cost problem of highly energy-consuming bring of hydrometallurgic recovery to a certain extent while process is more environmentally-friendly, also there are comparable market prospects while reducing pollution.
Description
Technical field
The invention belongs to waste lead acid battery resource utilization process fields, more particularly, to a kind of waste lead acid battery
Processing method for resource recovery.
Background technique
For comparing traditional pyrometallurgical smelting recycling lead technology, hydrometallurgic recovery waste lead acid battery is due to its reaction condition temperature
With discharge pollutants less, lead recovery is high the features such as be considered as a kind of environmentally friendly lead recovery technology, but since it is in reality
The some shortcomings still remained in the application process of border become it and are widely used in keeping in check for lead recycling industry.Chinese patent (Shen
It number please 201110293590.8) point out, wet process lead recovery technology is primarily present following problems:
1, pre-oxidation reduction reaction process takes a long time, while consuming a large amount of Pb, Fe and SO2Equal reducing agents and sulfuric acid, no
The cost of the step is increased only, and also increases the processing cost of subsequent alkaline desulfurization；
2, power consumption is relatively high, and the electrolytic cell pressure of electrolytic process is 2.7-3.2V, and the energy consumption of lead per ton is typically about 700-
950KWh；
3, the lead ion for remaining higher concentration in reduction process and electrolysis waste solution is pre-oxidized, this not only has equipment larger
Corrosivity, and it is larger to the murder by poisoning of environment；
4, anode reduces the recovery efficiency of lead with a large amount of brown lead oxide by-product is precipitated in electrolytic process, and
Cause secondary reduction processing load very big.
Generally speaking, it is low (mainly by high processing cost institute can be divided into income for wet process lead recycling problem encountered
Cause), part by-product almost without utility value and be likely to form pollution two aspect.In recent years there are many patents and correlation to grind
Study carefully and improvement is made that wet process lead removal process for subproblem, but few patented technologies can solve simultaneously they.?
Among this, the generation of by-product brown lead oxide is receive significant attention the phenomenon that.Traditional wet process lead recovery process process
It usually converts waste lead acid battery to by chemical reaction the divalent aqueous solution of lead, then is turned lead (II) ion by electrolysis means
Turn to lead bullion and brown lead oxide.Brown lead oxide obtained in usual wet process is considered as being worth not high by-product or as shadow
The intermediate product for ringing lead recycling yield is subsequently processed: Chinese patent (application number 201680041675.8) is with reducing agent by dioxy
Change lead reduction to form lead monoxide, lead monoxide, which merges to be formed with lead ion solution, combines lead ion solution, to realize not
Accumulate the continuous processing of brown lead oxide.Chinese patent (application number 201110293590.8) is penetrated using the selectivity of cationic membrane
Principle prevents from generating by-product brown lead oxide at electrolytic process Anodic, and switchs to generate industrial useful by-product oxygen.
Chinese patent (CN 101831668A) is by densification α-PbO obtained by electrodeposition process Anodic2Lead acid storage battery is directly used as after levigate
Pond anode raw material or additive.These technical solutions increase cost a bit, extend process, are easy to cause secondary pollution, have
It is a little then not by the value maximization of brown lead oxide.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of recyclings of waste lead acid battery to return
Receiving processing method is converted into methane sulfonic acid lead solution by the way that waste lead acid battery first to be carried out to wet-treating, then by the solution
It is electrolysed as electrolyte, cathode obtains high-purity lead bullion, and anode obtains the ti-supported lead dioxide electric coating with high added value
Electrode.The present invention is combined by that will innovate wet process lead recovery process with lead dioxide electrode preparation process, reduces useless by-product
Object improves the added value of recovery product while generation, thus solve to produce during the recovery processing of prior art waste lead acid battery
It is raw it is at high cost, process is long, is easy to cause secondary pollution, and the technical issues of not by the value maximization of brown lead oxide.
To achieve the above object, according to one aspect of the present invention, a kind of resource utilization of waste lead acid battery is provided
Processing method includes the following steps:
(1) waste lead acid battery is mixed with sulfuric acid solution and hydrogenperoxide steam generator, is sufficiently reacted, separation of solid and liquid obtains solid phase
And liquid phase, solid phase are lead sulfate, contain sulfuric acid and hydrogen peroxide in liquid phase；
(2) lead sulfate that step (1) obtains is obtained into solid phase and liquid with separation of solid and liquid after sodium hydroxide solution hybrid reaction
Phase, solid phase are lead hydroxide, and liquid phase is metabisulfite solution；
(3) lead hydroxide obtained using methane sulfonic acid leaching step (2), obtains methane sulfonic acid lead water solution；
(4) electro-deposition is carried out to the methane sulfonic acid lead water solution that step (3) obtain, anode obtains ti-supported lead dioxide electric coating
Electrode, cathode obtain elementary lead.
Preferably, step (1) further include: use platinized platinum as catalyst the liquid phase, peroxide in heating induction liquid phase
Change hydrogen to decompose, so that only containing sulfuric acid solution in the liquid phase.
Preferably, step (2) further include: the liquid phase metabisulfite solution is translated by the method for diaphragm electrolysis
Sulfuric acid and sodium hydroxide.
Preferably, the concentration of step (1) described sulfuric acid solution is 1~3mol/L, wherein sulfuric acid and the waste lead acid battery
The molar ratio of middle lead element is 1~1.5:1；The concentration of the hydrogenperoxide steam generator is 0.8~1.5mol/L, the hydrogen peroxide
Molar ratio with lead element in the waste lead acid battery is 0.4~0.8:1.
Preferably, the concentration of step (2) described sodium hydroxide solution is 0.01~1mol/L, the sodium hydroxide and the sulphur
The ratio between lead plumbate mole is 2.5~3:1.
Preferably, during step (3) methane sulfonic acid leaching lead hydroxide, the methane sulfonic acid and lead hydroxide rub
, than being 2.2:1~3:1, leaching temperature is 50 DEG C~70 DEG C for you, the concentration of the aqueous solution of methanesulfonic be 2.2mol/L~
2.5mol/L。
Preferably, the condition of step (4) described electro-deposition are as follows: first with anodic current density for 10~20mA/cm2, electric heavy
Accumulated temperature degree is 10~25 DEG C, and electrode spacing is 1.5cm~2cm, and electrodeposit liquid group becomes concentration and is maintained at 0.8~1.2mol/L's
The methane sulfonic acid lead water solution carries out 20min~30min electro-deposition；It is again 40mA/cm with anodic current density2~60mA/
cm2, electrodeposition temperature is 60~80 DEG C, electrode spacing 1.5cm, and electrodeposit liquid group becomes concentration and is maintained at 0.8~1.2mol/
2~3h of the methane sulfonic acid lead water solution electro-deposition of L.
Preferably, step (4) described electro-deposition uses the titanium material of surface coating tin-antimony oxide as anode, the sun
Great body obtains by the following method: the titanium dioxide prior to the entire titanium material surface of heating etching removal in oxalic acid aqueous solution is blunt
Change layer, reusable heat decompose method titanium material institute it is in need it is subsequent carry out be electroplated brown lead oxide surface location coated with tin antimony oxygen
Compound, using graphite flake, copper sheet, titanium sheet, stainless steel substrates or platinized platinum as cathode.
Preferably, the diaphragm that the diaphragm electrolysis uses is Nafion212 perfluorinated sulfonic acid cation-exchange membrane, electrolytic condition
Control is 30 DEG C~60 DEG C in temperature range, current density range 30mA/cm2~60mA/cm2。
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) present invention is a kind of environmentally friendly lead recovery technology, and each section product in removal process can be by
It re-uses, is nearly free from pollution, while generating high added value.For relatively other wet process lead recovery technologies, the present invention
Solve that generation pollution, portion of product added value is high, these three low main problems of income simultaneously.Especially for income,
Since product (sulfuric acid, sodium hydroxide and ti-supported lead dioxide electric coated electrode) of the present invention in addition to lead bullion can equally be created
A large amount of added value, this can to a certain degree solve hydrometallurgic recovery lead high cost problem, thus make hydrometallurgic recovery lead this
In contrast more environmentally-friendly recovery technology can be more widely used class.
(2) present invention is converted into methane sulfonic acid lead solution by the way that waste lead acid battery first to be carried out to wet-treating, then should
Solution is electrolysed as electrolyte, and cathode obtains high-purity lead bullion, and anode obtains the ti-supported lead dioxide electric with high added value
Coated electrode.By controlling the technological parameters such as the condition of electro-deposition and the concentration of methane sulfonic acid lead, good bonding strength is obtained
Brown lead oxide coating.
(3) recovery and treatment method of waste lead acid battery of the present invention can carry out in laboratory and factory；In laboratory
It carries out, convenient for the inspection and test to product.It carries out, can be mass-produced in factory, improve production efficiency, reduction is produced into
This.
(4) the ti-supported lead dioxide electric coated electrode obtained using the processing method for resource recovery of waste lead acid battery of the present invention
It can be used as the anode during electro-catalysis sewage, electroplating sludge dehydration or electro-deposition recycling copper, experiments have shown that its working performance is good
It is good.
Detailed description of the invention
Fig. 1 is the processing method for resource recovery flow diagram of waste lead acid battery of the present invention；
Fig. 2 is that embodiment 1 recycles the α-brown lead oxide middle layer electron microscope in the lead dioxide electrode of lead preparation
Figure；
Fig. 3 is that embodiment 1 recycles β-brown lead oxide surface layer electron microscope picture in the lead dioxide electrode of lead preparation；
Fig. 4 is the X-ray diffractogram that embodiment 1 recycles titanium dioxide lead layer in the lead dioxide electrode of lead preparation；
Fig. 5 is the lead dioxide electrode that embodiment 1 recycles lead preparation and business electrode for H during H acid catalyzed degradation
Sour removal rate compares figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The processing method for resource recovery of a kind of waste lead acid battery provided by the invention, as shown in Figure 1, including following step
It is rapid:
(1) waste lead acid battery is mixed with sulfuric acid solution and hydrogenperoxide steam generator, is sufficiently reacted, separation of solid and liquid obtains solid phase
And liquid phase, solid phase are lead sulfate, contain sulfuric acid and hydrogen peroxide in liquid phase.
The chemical equation to react is respectively as follows:
PbO2+Pb+2H2SO4→2PbSO4+2H2O
PbO2+H2O2+H2SO4→PbSO4+O2+2H2O
In some embodiments, the concentration of step (1) described sulfuric acid solution is 1~3mol/L, wherein sulfuric acid and the scrap lead
The molar ratio of lead element is 1~1.5:1 in sour battery；The concentration of the hydrogenperoxide steam generator is 0.8~1.5mol/L, the mistake
The molar ratio of lead element is 0.4~0.8:1 in hydrogen oxide and the waste lead acid battery.
(2) lead sulfate that step (1) obtains is obtained into solid phase and liquid with separation of solid and liquid after sodium hydroxide solution hybrid reaction
Phase, solid phase are lead hydroxide, and liquid phase is metabisulfite solution.
In some embodiments, the concentration of step (2) described sodium hydroxide solution is 0.01~1mol/L, the sodium hydroxide with
The ratio between described lead sulfate mole is 2.5~3:1.It is added after sodium hydroxide plus water is adjusted to solid-to-liquid ratio 1:8~1:10 or so, after
With sulfuric acid tune pH to 8 or so.
(3) lead hydroxide obtained using methane sulfonic acid leaching step (2), obtains methane sulfonic acid lead water solution.
Lead hydroxide is leached using methane sulfonic acid, the aqueous solution of methane sulfonic acid lead is obtained, then the solution is electrolysed,
The purpose of selection methane sulfonic acid root is can be to discharge in circulating and recovering and cyclic process without the compound for being unfavorable for environment.First simultaneously
Base sulfonic acid is nontoxic and can degrade in nature as organic acid, is a kind of environmentally friendly reactant.
In some embodiments, during step (3) methane sulfonic acid leaches lead hydroxide, the methane sulfonic acid and hydroxide
The molar ratio of lead is 2.2:1~3:1, and leaching temperature is 50 DEG C~70 DEG C, and the concentration of the aqueous solution of methanesulfonic is 2.2mol/
L~2.5mol/L.
(4) electro-deposition is carried out to the methane sulfonic acid lead water solution that step (3) obtain, anode obtains ti-supported lead dioxide electric coating
Electrode, cathode obtain elementary lead.
In some embodiments, the condition of step (4) described electro-deposition are as follows: first with anodic current density for 10~20mA/
cm2, electrodeposition temperature is 10~25 DEG C, and electrode spacing is 1.5cm~2cm, electrodeposit liquid group become concentration be maintained at 0.8~
The methane sulfonic acid lead water solution of 1.2mol/L carries out the electro-deposition of 20min~30min, to obtain among α-brown lead oxide
Layer；It is again 40mA/cm with anodic current density2~60mA/cm2, electrodeposition temperature is 60~80 DEG C, electrode spacing 1.5cm,
Electrodeposit liquid group becomes the methane sulfonic acid lead water solution 2~3h of electro-deposition that concentration is maintained at 0.8~1.2mol/L, to obtain
β-brown lead oxide surface layer.
Cathode material selects graphite flake, copper sheet, titanium sheet, stainless steel substrates or platinized platinum, and electrodeposition condition temperature is identical as anode,
Current density is by control cathode electrode area control in 10mA/cm2~200mA/cm2, by selecting special material substrate, control
Leaching mode, plumbum ion concentration, electrodeposition temperature and current density processed regulate and control anodic deposition, make the brown lead oxide coated areas obtained
The anode of lead dioxide mud that not will form usually in traditional electrolyte lead recovery process has good adhesive force and fine and close journey
Degree, while the microscopic appearance of brown lead oxide coating can be accurately controlled and crystalline structure makes it as the organic dirt of Electrocatalysis Degradation
Have and degradation capability similar in business electrode when contaminating the anode of object process.
In some embodiments, step (4) uses the titanium material of surface coating tin-antimony oxide as anode, the titanium material
Prior to the titanium dioxide passivation layer that heating etching in oxalic acid aqueous solution removes entire titanium material surface, the method that reusable heat decomposes exists
Titanium material it is in need it is subsequent carry out plating brown lead oxide surface location coating tin-antimony oxide, cathode material use graphite
Piece, copper sheet, titanium sheet, stainless steel substrates or platinized platinum.
Brown lead oxide is made into high quality electrode coating by the present invention, the most important index parameter of the two o'clock of consideration: 1, catalysis is lived
Property (mainly being determined by the crystalline structure of brown lead oxide)；2, service life (mainly the binding force by brown lead oxide in substrate with
The compactness extent of titanium dioxide lead layer itself determines).The present invention passes through control sedimentary condition temperature, the group of current density and electrolyte
At ingredient (such as in electrolyte lead ion concentration, the concentration of methane sulfonic acid root, the pH and electrolyte of electrolyte in electrolyte
In whether there is other impurities ion) obtain the lead dioxide electrode coating with excellent catalytic activity and service life.
In electrolytic recovery plumbing, the control of temperature and current density serves the deposition of elementary lead without in view of two
Lead oxide.The lead electrolytic solutions of many recycling lead processes concentration of lead in water in electrolytic process reduces always with time course
To zero, and the present invention claims concentration of electrolyte need to maintain a stable state, with it is lasting acquisition quality it is uniform two
Lead oxide.Electrolyte methane sulfonic acid lead used in the present invention is the lead hydroxide that is handled with lead plaster with methane sulfonic acid simultaneously
It leaches, research shows that (temperature etc.) condition can determine saturation solubility of the lead in methane sulfonic acid in leaching process, in turn
Institute's expense of methane sulfonic acid in solution is influenced when dissolving same plumbum ion concentration, and the amount for testing discovery methane sulfonic acid is also
Influence the key factor of brown lead oxide binding force index.The methane sulfonic acid lead that electroplating industry uses is ready-made technical grade purity,
And methane sulfonic acid lead of the invention is that salvage material leaches to obtain, and needs to overcome impurity, lead and methane sulfonic acid molar ratio etc. several
Problem.
In addition to this, anode select coating tin-antimony oxide do bottom titanium substrate do bottom be also the present invention obtain it is high-quality
A key factor of brown lead oxide is measured, tin-antimony oxide does bottom and is conducive to increase titanium dioxide lead layer and titanium substrate binding force,
And routine recycles anode graphite, titanium, the steel mesh etc. that lead uses, obtained brown lead oxide is often the caducous earth of positive pole.
(5) use platinized platinum as catalyst step (1) described liquid phase, hydrogen peroxide decomposes in heating induction liquid phase, makes
This also only contains sulfuric acid solution in phase；
(6) sulfuric acid and hydrogen are translated by the method for diaphragm electrolysis to liquid phase metabisulfite solution described in step (2)
Sodium oxide molybdena.
In some embodiments, the amberplex that step (6) described diaphragm electrolysis uses is preferably Nafion212 perfluor sulphur
Sour cation-exchange membrane, electrolytic condition control are 30 DEG C~60 DEG C in temperature range, current density range 30mA/cm2~
60mA/cm2.The chemical equation of diaphragm electrolysis is
Na2SO4+2H2O→2NaOH+H2SO4
According to the ti-supported lead dioxide electric coated electrode that the above method of the present invention processing waste lead acid battery obtains, it can be used as electricity and urge
Change the anode during sewage, electroplating sludge dehydration or electro-deposition recycling copper.As electrode coating, brown lead oxide is a kind of performance
The brown lead oxide generated in removal process can be applied directly as electrode coating material, will have pole by excellent material
High added value, and the value created from brown lead oxide coated electrode can also subsidize in turn input by wet-treating
Sky high cost is easier to this environmentally friendly lead resource recovery technology to improve the income of hydrometallurgic recovery lead overall process
Received by industrial circle.
Waste lead acid battery is processed by the present invention by the innovation wet processing that whole process does not generate extra low value by-product
It for high-purity methylsulfonic acid lead, and is electrolysed using this methane sulfonic acid lead as electrolyte, cathode obtains high-purity lead bullion, anode
Obtain the ti-supported lead dioxide electric coated electrode with high added value.The present invention will be by that will innovate wet process lead recovery process and titanium dioxide
Lead electrode preparation process combines, and reduces the added value that recovery product is improved while unwanted byproduct generates.Process more
Add the high cost problem of highly energy-consuming bring for solving hydrometallurgic recovery while environmental protection to a certain extent, reduces the same of pollution
When also there are comparable market prospects.
The following are embodiments:
Embodiment 1:
The lead plaster that 100g is obtained from waste lead acid battery is taken, the sulfuric acid that 250mL concentration is 2mol/L is successively added thereto
(wherein sulfur acid stannous 0.001mol) and 100mL concentration are that the aqueous hydrogen peroxide solution constant volume of 1mol/L is water-soluble at 1000ml
Liquid leaches 1h under conditions of stirring.The sodium hydroxide solution that 2L concentration is 0.5mol/L is added after separation of solid and liquid into filter residue,
PH to 8 or so is adjusted with sulfuric acid, 1h is leached under conditions of stirring, after being separated by filtration, 400mL concentration, which is added, to white precipitate is
2.1mol methane sulfonic acid operation temperature be 60 DEG C under conditions of be stirred continuously, pass through again after being completely dissolved to white precipitate
Concentration adjusts to obtain the methane sulfonic acid lead of 1mol/L, which prepares ti-supported lead dioxide electric pole for lower single order simultaneously
With electrolyte is done during lead bullion.Separately take the grass that the titanium sheet having a size of 20 × 45 × 0.5mm is 10% in 200mL mass fraction
2h is etched in acid solution, temperature of heating plate is set as 140 DEG C, and etching terminates to be placed on spare in n-butanol.It is taken from n-butanol
Bottom is brushed in titanium substrate using coating liquid after titanium substrate out, wherein coating liquid by 175mL n-butanol, 75mL concentrated hydrochloric acid,
The ratio of 58.9g stannic chloride pentahydrate and 9.575g antimony trichloride is configured to the mixed solution of 250mL, brushes use hairbrush every time
Substrate is applied completely after dipping mixed solution.It according to said method repeats to brush bottom 4 times, prior under infrared lamp after brushing every time
120 DEG C of drying, with 500 DEG C of roasting 10min in Muffle furnace, are changed to roast under conditions of 500 DEG C for the last time in Muffle furnace
Burn 1h.Using the processed titanium substrate of the process as the anode of electrolytic process, copper sheet utilizes the methane sulfonic acid as cathode
Lead is electrolysed as electrolyte, deposits brown lead oxide coating and lead bullion in anode and cathode respectively.Specific sedimentary condition
Are as follows: electrolyte formula: the methane sulfonic acid lead of 1mol/L is first 20mA/cm with current density2, electrodeposition temperature is 25 DEG C, electrode
The condition that spacing is 1.5cm deposits half an hour, after with current density be 50mA/cm2, electrodeposition temperature is 50 DEG C, electrode spacing
It is deposited two hours for the condition of 1.5cm.
The sodium sulphate filtrate for taking second of separation of solid and liquid to obtain, carries out diaphragm electrolysis, and filter membrane uses Nafion212 perfluor sulphur
Sour cation-exchange membrane, anode are DSA inertia titanium net, and cathode is gray cast iron piece, to be saturated sodium sulphate as anolyte, sodium hydroxide
Solution is catholyte, and control temperature is between 60~80 DEG C in electrodeposition temperature, and current density is in 30mA/cm2~200mA/cm2
Between, electrolysis time two hours.Sulfuric acid and sodium hydroxide are obtained in anode and cathode respectively, sodium hydroxide carries out reuse, sulfuric acid
Part reuse is partially sold as product.
With anodic current density for 10~20mA/cm2, electrodeposition temperature be 10~25 DEG C, electrode spacing be 1.5cm~
2cm, electrodeposit liquid group become concentration be maintained at 0.8~1.2mol/L the methane sulfonic acid lead water solution carry out 20min~
What the process of 30min electro-deposition obtained is α-brown lead oxide middle layer；It is again 40mA/cm with anodic current density2~60mA/
cm2, electrodeposition temperature is 60~80 DEG C, electrode spacing 1.5cm, and electrodeposit liquid group becomes concentration and is maintained at 0.8~1.2mol/
2~3h of the methane sulfonic acid lead water solution electro-deposition of L is then the β-brown lead oxide deposited in α-brown lead oxide middle layer
Surface layer.α-brown lead oxide middle layer effect is the company of playing between tin-antimony oxide bottom and β-brown lead oxide surface layer of titanium substrate
The effect connect, and then improve β-binding force of the brown lead oxide surface layer in substrate.β-brown lead oxide surface layer is then determining electrode electricity
The material of catalytic performance.
Its crystal structure of the coating for the brown lead oxide that the embodiment obtains is as shown in Figures 2 to 4, and Fig. 2 is the α-titanium dioxide
The electron microscope picture of lead middle layer, Fig. 3 are β-brown lead oxide surface layer electron microscope picture, and Fig. 4 is that the X of titanium dioxide lead layer is penetrated
Ray diffraction diagram.As can be seen that the anode of lead dioxide often occurred compared to anode after being electrolysed in conventional wet lead removal process
Mud, brown lead oxide coating obtained in this example have a fine and close, complete, continuous contour structures, while can be according to reacting item
Part is accurately controlled microscopic appearance and crystalline structure required for obtaining, can be as the brown lead oxide with practical value
Anodic coating.
The titanium-matrix electrode containing brown lead oxide coating that the anode is obtained is as the processing of H acid Electrocatalysis Degradation, specific side
Method are as follows: with 5mA/cm2Current density in 100cm2Recycling lead prepare electrode and electrolyte concentrations are respectively on business electrode
The H acid solution 1L of 500mg/L, by timing using spectrophotometric determination sample absorbance to determine removal rate, experimental result
As shown in Figure 5, it can be seen that in 32 hours Electrocatalysis Degradation treatment processes, recycling lead prepares electrode and business electrode performance
It is close.
It is tested and is found by constant-potential electrolysis sludge dewatering, recycling lead prepares lead dioxide electrode can be in certain voltage model
The moisture content of municipal sludge is dropped to 60% or less from 80%~85% in 10 minutes in enclosing.
Embodiment 2
The lead plaster that 800g is obtained from waste lead acid battery is taken, the sulfuric acid that 200mL concentration is 2mol/L is successively added thereto
(wherein sulfur acid stannous 0.01mol) and 800mL concentration are that the aqueous hydrogen peroxide solution constant volume of 1mol/L is water-soluble at 8000ml
Liquid leaches 1h under conditions of stirring.The sodium hydroxide solution that 8L concentration is 1mol/L is added after separation of solid and liquid into filter residue, uses
Sulfuric acid adjusts PH to 8 or so, and 1h is leached under conditions of stirring, and after being separated by filtration, 3L concentration is added to white precipitate
The methane sulfonic acid of 2.2mol is stirred continuously under conditions of operation temperature is 60 DEG C, again by dense after being completely dissolved to white precipitate
Degree adjustment obtain the methane sulfonic acid lead of 1mol/L, the methane sulfonic acid lead for lower single order simultaneously prepare ti-supported lead dioxide electric pole with
Electrolyte is done during lead bullion.Separately take the grass that the titanium net having a size of 100 × 100 × 1mm is 10% in 1500mL mass fraction
2h is etched in acid solution, temperature of heating plate is set as 190 DEG C, and etching terminates to be placed on spare in n-butanol.It is taken from n-butanol
Bottom is brushed in titanium substrate using coating liquid after titanium substrate out, wherein coating liquid by 175mL n-butanol, 75mL concentrated hydrochloric acid,
The ratio of 58.9g stannic chloride pentahydrate and 9.575g antimony trichloride is configured to the mixed solution of 250mL, brushes use hairbrush every time
Substrate is applied completely after dipping mixed solution.It according to said method repeats to brush bottom 5 times, prior under infrared lamp after brushing every time
120 DEG C of drying, with 500 DEG C of roasting 10min in Muffle furnace, are changed to roast under conditions of 500 DEG C for the last time in Muffle furnace
Burn 1h.Using the processed titanium substrate of the process as the anode of electrolytic process, copper sheet utilizes the methane sulfonic acid lead as cathode
It is electrolysed as electrolyte, deposits brown lead oxide coating and lead bullion in anode and cathode respectively.Specific sedimentary condition are as follows:
Electrolyte formula: the methane sulfonic acid lead of 1mol/L is first 20mA/cm with current density2, electrodeposition temperature is 20 DEG C, between electrode
Away from depositing half an hour for the condition of 1.5cm, after with current density be 50mA/cm2, electrodeposition temperature is 50 DEG C, and electrode spacing is
The condition of 1.5cm deposits two and one-half- hours.
The sodium sulphate filtrate for taking second of separation of solid and liquid to obtain, carries out diaphragm electrolysis, and filter membrane uses Nafion212 perfluor sulphur
Sour cation-exchange membrane, anode are DSA inertia titanium net, and cathode is gray cast iron piece, to be saturated sodium sulphate as anolyte, sodium hydroxide
Solution is catholyte, and control temperature is between 60~80 DEG C in electrodeposition temperature, and current density is in 30mA/cm2~200mA/cm2
Between, electrolysis time two hours.Sulfuric acid and sodium hydroxide are obtained in anode and cathode respectively, sodium hydroxide carries out reuse, sulfuric acid
Part reuse is partially sold as product.
Comparative example 1
Other conditions are with embodiment 1, the difference is that the methane sulfonic acid lead concentration that leaching lead hydroxide uses is 4mol/L, it is real
Observe that there are many Bubbles for anode surface within electro-deposition incipient a period of time in testing.Finally obtained coating combines
Power is poor compared with embodiment 1, thus it is speculated that brown lead oxide is in the deposition process of Titanium base surface due to analysing oxygen side reaction in this comparative example
More acutely, the oxygen bubbles being precipitated is caused to influence the early stage nucleation process of early stage nucleation of brown lead oxide, so as to cause titanium dioxide
Binding force is low between lead and substrate.
The brown lead oxide of traditional lead dioxide electrode preparation process preparation needs to deposit the titanium dioxide of two kinds of crystalline structures of α, β
Lead, α brown lead oxide is as bottom, and beta lead dioxide is as surface layer.In common research, the brown lead oxide of both crystal forms is needed
It to be prepared under different sedimentary conditions (temperature, current density, PH etc.).Wherein pH both be one of sedimentary condition it is main not
Same, i.e., α brown lead oxide generally tends to grow in alkali plating solution, and beta lead dioxide generally tends to raw in acidic bath
Long, this makes general lead dioxide electrode preparation respectively using the dioxy of different two kinds of different crystal forms structures of bath deposition
Change lead (such as Chinese patent CN 108217852A, the bath deposition α dioxy using electroplate liquid formulation containing sodium hydroxide and lead oxide
Change lead layer, the bath deposition beta lead dioxide layer using electroplate liquid formulation containing plumbi nitras).However present invention selection is with methane sulfonic acid
Lead solution, can be in same electroplate liquid formulation only by changing the accurate control respectively of the conditions such as temperature and current density as plating solution
The brown lead oxide of two different crystalline structures is made.Make the step of being electrolysed while generating lead bullion and brown lead oxide coating operation
Condition is easier, easy to control.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of processing method for resource recovery of waste lead acid battery, which comprises the steps of:
(1) waste lead acid battery is mixed with sulfuric acid solution and hydrogenperoxide steam generator, is sufficiently reacted, separation of solid and liquid obtains solid phase and liquid
Phase, solid phase are lead sulfate, contain sulfuric acid and hydrogen peroxide in liquid phase；
(2) lead sulfate that step (1) obtains is obtained into solid phase and liquid phase with separation of solid and liquid after sodium hydroxide solution hybrid reaction, Gu
It is mutually lead hydroxide, liquid phase is metabisulfite solution；
(3) lead hydroxide obtained using methane sulfonic acid leaching step (2), obtains methane sulfonic acid lead water solution；
(4) electro-deposition is carried out to the methane sulfonic acid lead water solution that step (3) obtain, anode obtains ti-supported lead dioxide electric coating electricity
Pole, cathode obtain elementary lead.
2. processing method as described in claim 1, which is characterized in that step (1) further include: made to the liquid phase using platinized platinum
For catalyst, hydrogen peroxide is decomposed in heating induction liquid phase, so that only containing sulfuric acid solution in the liquid phase.
3. processing method as described in claim 1, which is characterized in that step (2) further include: to the liquid phase metabisulfite solution
Sulfuric acid and sodium hydroxide are translated by the method for diaphragm electrolysis.
4. processing method as described in claim 1, which is characterized in that the concentration of step (1) described sulfuric acid solution be 1~
3mol/L, wherein the molar ratio of sulfuric acid and lead element in the waste lead acid battery is 1~1.5:1；The hydrogenperoxide steam generator
Concentration is 0.8~1.5mol/L, and the molar ratio of lead element is 0.4~0.8:1 in the hydrogen peroxide and the waste lead acid battery.
5. processing method as described in claim 1, which is characterized in that the concentration of step (2) described sodium hydroxide solution is
0.01~1mol/L, the ratio between the sodium hydroxide and the lead sulfate mole are 2.5~3:1.
6. processing method as described in claim 1, which is characterized in that the process of step (3) methane sulfonic acid leaching lead hydroxide
In, the molar ratio of the methane sulfonic acid and lead hydroxide is 2.2:1~3:1, and leaching temperature is 50 DEG C~70 DEG C, the methyl sulphur
The concentration of aqueous acid is 2.2mol/L~2.5mol/L.
7. processing method as described in claim 1, which is characterized in that the condition of step (4) described electro-deposition are as follows: first with anode
Current density is 10~20mA/cm2, electrodeposition temperature is 10~25 DEG C, and electrode spacing is 1.5cm~2cm, electrodeposit liquid composition
The methane sulfonic acid lead water solution for being maintained at 0.8~1.2mol/L for concentration carries out 20min~30min electro-deposition；Again with sun
Electrode current density is 40mA/cm2~60mA/cm2, electrodeposition temperature is 60~80 DEG C, electrode spacing 1.5cm, electrodeposit liquid group
2~3h of the methane sulfonic acid lead water solution electro-deposition of 0.8~1.2mol/L is maintained at as concentration.
8. processing method as described in claim 1, which is characterized in that step (4) electro-deposition uses surface tin coating antimony
The titanium material of oxide is obtained as anode, the anode especially by following method: prior to heating etching in oxalic acid aqueous solution
The titanium dioxide passivation layer of entire titanium material surface is removed, the method that reusable heat decomposes is in titanium material institute subsequent progress electricity in need
The surface location for plating brown lead oxide applies tin-antimony oxide, using graphite flake, copper sheet, titanium sheet, stainless steel substrates or platinized platinum as yin
Pole.
9. processing method as claimed in claim 3, which is characterized in that the diaphragm that the diaphragm electrolysis uses is Nafion212
Perfluorinated sulfonic acid cation-exchange membrane, electrolytic condition control are 30 DEG C~60 DEG C in temperature range, current density range 30mA/
cm2~60mA/cm2。
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